EP2938713A2 - Lubrifiants à ultra faible teneur en cendres sulfatées, phosphore et soufre pour des moteurs à combustion interne - Google Patents

Lubrifiants à ultra faible teneur en cendres sulfatées, phosphore et soufre pour des moteurs à combustion interne

Info

Publication number
EP2938713A2
EP2938713A2 EP13867703.4A EP13867703A EP2938713A2 EP 2938713 A2 EP2938713 A2 EP 2938713A2 EP 13867703 A EP13867703 A EP 13867703A EP 2938713 A2 EP2938713 A2 EP 2938713A2
Authority
EP
European Patent Office
Prior art keywords
aromatic dicarboxylic
lubricating oil
dicarboxylic acid
oil composition
less
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP13867703.4A
Other languages
German (de)
English (en)
Other versions
EP2938713A4 (fr
Inventor
Katsumi Umehara
Willem Van Dam
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chevron Japan Ltd
Chevron Oronite Co LLC
Original Assignee
Chevron Japan Ltd
Chevron Oronite Co LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chevron Japan Ltd, Chevron Oronite Co LLC filed Critical Chevron Japan Ltd
Publication of EP2938713A2 publication Critical patent/EP2938713A2/fr
Publication of EP2938713A4 publication Critical patent/EP2938713A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
    • C10M141/06—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic nitrogen-containing compound
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/142—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M2215/06—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to carbon atoms of six-membered aromatic rings
    • C10M2215/066—Arylene diamines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/223—Five-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/28—Amides; Imides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/42—Phosphor free or low phosphor content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/43—Sulfur free or low sulfur content compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/40—Low content or no content compositions
    • C10N2030/45—Ash-less or low ash content
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition

Definitions

  • the present invention generally relates to Ultra-Low SAPS lubricants for Internal
  • the catalysts utilized can be poisoned when they interact with certain metals or phosphorus.
  • Limitations on sulfated ash, phosphorus, and sulfur levels (SAPS) in motor oils have been put in place to enable the use of exhaust gas after-treatment devices.
  • Commercial lubricants for internal combustion engines are commonly formulated in such a way that the SAPS content of the lubricant falls just below those limits. It is assumed by those skilled in the art of formulating engine lubricants that lowering the treat rates of SAPS containing performance additives far below those restrictions causes the performance of the lubricant to deteriorate to the point of unacceptability. In addition to the CO and particle limits on emissions, there are efforts being made to reduce carbon dioxide (CO 2 ) emissions from vehicles.
  • CO 2 carbon dioxide
  • U.S. Patent Application No. 20030224948 discloses an additive formulation comprising one or more ec -treated dispersants, borated dispersants, and a dispersed aromatic dicarboxylic acid corrosion inhibitor; a dispersant inhibitor package comprising one or more ec -treated dispersants, borated dispersants, and a dispersed aromatic dicarboxylic acid corrosion inhibitor; a lubricating oil comprising said dispersant inhibitor package; and a method for lubricating engines.
  • 20100152079 discloses a lubricant composition containing an oil of lubricating viscosity, a ,N,N',N'-tetramethyl-naphthalene-l,8-diamine, and at least one additive selected from antioxidants, detergents, dispersants which together provide superior oxidation inhibition for automotive and truck crankcase lubricants.
  • U. S. Patent Application No. 20080139425 discloses an additive package, useful in a lubricant composition, which comprises: a diluent; and a hydrocarbyl substituted triazole compound, with the proviso that the lubricant is substantially free of compounds containing phosphorus.
  • This additive package is selected for its ability to protect lead and silver bearings found in medium speed diesel engines including railroad engines.
  • European Patent Application No. 0758016 discloses an additive combination comprising an aromatic amine anti-oxidant and a "B" compound.
  • the combination contains 1 pt. wt. of boron per 250 pts. of nitrogen in the amine.
  • the oils exemplified are blended with a standard additive package and are not essentially free of SAPS derived from the components.
  • U. S. Patent Application No. 20080020953 discloses a lubricating oil composition which contains lube base oil comprising mineral oil and/or synthetic oil, ash- free dispersant (in mass%) (0.01-0.14) based on nitrogen amount, antioxidant and sulfated ash (1.2 or less).
  • the antioxidant contains dialkyldiphenyl amine (0.3-5) and hindered phenol compound (0-2.5).
  • the dispersant contains alkenyl- or alkyl-succinimide and/or boron compound derivative (0.05 or less) in terms of nitrogen amount. All example oils contain approximately 1% Sulfated Ash (SASH).
  • U. S. Patent No. 7,026,273 discloses a crankcase lubricating oil composition, for an internal combustion engine, which comprises an admixture of oil and boron-containing additive, and preset amounts of phosphorus and sulfur.
  • This patent family teaches lubricating oil compositions containing (a) a boron-containing additive and one or more co-additives, wherein the lubricating oil composition has greater than 200 ppm by mass of boron, less than 600 ppm by mass of phosphorus and less than 4000 ppm by mass of sulfur, based on the mass of the oil composition. All example lubricants contain approximately 1% SASH.
  • U. S. Patent Application No. 20060058200 discloses a lubricating oil composition for internal combustion engines, which contains a major amount of oil of lubricating viscosity, (a) at least one nitrogen-containing dispersant, the dispersant providing to the oil a nitrogen content of at least 0.075 wt. % nitrogen, the dispersant having a polyalkenyl backbone which has a molecular weight range of about 900 to 3000, and (b) an oil soluble or oil dispersible source of boron, present in an amount so as to provide a ratio of wt. % nitrogen to wt.
  • oils are low SAPS, but not significantly below the current mandated levels. They still contain ZnDTP and metal detergents.
  • Japanese Patent No. 2922675 discloses a lubricating oil composition for coping with strict regulation of exhaust gas which contains 0.5-8 wt.% a (3,5-di-tert-butyl-4- hydroxyphenol) carboxylic acid alkyl ester(s) as an ash-free cleaner, 3-12 wt.% succinimide type ash- free dispersant(s) and 0.1-3 wt.% phenol type ash- free antioxidant(s) in a lubricating base oil comprising a mineral and a synthetic oil(s). These lubricants are designed to not precipitate when in contact with methanol fuel.
  • U. S. Patent Application No. 20080020952 discloses a lubricant oil composition for contacting metal materials containing lead which comprises a lubricant base oil, an optional zinc dithiophosphate present in 0.08 wt% or less, and an additive selected from organic molybdenum compound excluding molybdenum thiophosphate, boric acid ester and/or derivatives, a mixture of the two, or organic molybdenum compound, boric acid modified alkyl or alkenyl succinic acid imide. These oils are low in Zn salts, but still contain metallic detergents.
  • 20060009366 discloses an oil composition for lubricating internal combustion engines which comprises base oil and at least 1.4 wt% of an aminic and/or phenolic antioxidant, wherein said lubricating oil composition is phosphorus free.
  • These lubricants are formulated to be free of phosphorus antiwear additives, but are not free of metallic detergents. They are neither low ash nor low sulfur.
  • U. S. Patent Application No. 20040106527 discloses a lubricating oil composition for use in internal combustion engines, used along with a gasoline fuel having sulfur content of less than 10 ppm by weight, which has a phosphorous content of no more than 0.05 wt.%. These lubricants are again low P without limiting sulfur or ash.
  • the currently existing lubricants have Low SAPS restrictions including: sulfated ash limits of ⁇ 0.8 wt% for PCMO (Passenger Car Motor Oil) or ⁇ 1.0 wt% for HDEO (Heavy Duty Engine Oil); phosphorus limits of ⁇ 0.08 wt% for both PCMO and HDEO; and sulfur limits of ⁇ 0.3 wt% for both PCMO and HDEO.
  • SAPS levels derived from the components in the additive package can be essentially zero.
  • Ultra-Low SAPS' lubricating oil compositions are defined as: lubricating oil compositions wherein Sulfur is present at less than 1000 ppm, Phosphorous is present at less than 300 ppm, and Sulfated Ash is present at less than 0.25 wt%.
  • S is present at ⁇ 1000 ppm, ⁇ 800 ppm, ⁇ 500 ppm, ⁇ 300 ppm, ⁇ 100 ppm, ⁇ 50 ppm, ⁇ 10 ppm, and could be zero
  • P is present at ⁇ 300 ppm, ⁇ 200 ppm, ⁇ 100 ppm, ⁇ 50 ppm, ⁇ 10 ppm, and could be zero
  • Sulfated Ash is present as ⁇ 0.25 wt%, ⁇ 0.20 wt%, ⁇ 0.15 wt%, ⁇ 0.10 wt%, ⁇ 0.05wt%, ⁇ 0.01 wt% and could be 0 wt% in the finished lubricant.
  • the lubricating oil composition contains less than 800 ppm sulfur, less than 200 ppm phosphorous, and less than 0.20 wt% sulfated ash.
  • the lubricating oil composition contains less than 500 ppm sulfur, less than 100 ppm phosphorous, and less than 0.15 wt% sulfated ash.
  • the lubricating oil composition contains less than 300 ppm sulfur, less than 50 ppm phosphorous, and less than 0.10 wt% sulfated ash. In one embodiment of the present invention the lubricating oil composition contains less than 100 ppm sulfur, 0 ppm phosphorous, and less than 0.05 wt% sulfated ash.
  • the lubricating oil composition contains less than 50 ppm sulfur, 0 ppm phosphorous, and less than 0.05 wt% sulfated ash.
  • an ultra-low SAPS lubricating oil composition comprising:
  • an aromatic dicarboxylic acid treated dispersant supplying at least 0.30 wt. % aromatic dicarboxylic acid to said lubricating oil composition
  • an ashless peroxide decomposer present at a treat rate of from about 0.4 to 5.0 wt%; a metal deactivator wherein the metal deactivator is present at a treat rate of greater than 0.08 wt%;
  • said lubricating oil composition contains less than 1000 ppm sulfur, less than 300 ppm phosphorus and less than 0.25 wt% sulfated ash.
  • a method of lubricating an engine with an ultra-low SAPS lubricating oil composition comprising:
  • an aromatic dicarboxylic acid treated dispersant supplying at least 0.30 wt. % aromatic dicarboxylic acid to said lubricating oil composition
  • an ashless peroxide decomposer present at a treat rate of from about 0.4 to 5.0 wt%; a metal deactivator wherein the metal deactivator is present at a treat rate of greater than 0.08 wt%; wherein said lubricating oil composition contains less than 1000 ppm sulfur, less than 300 ppm phosphorus and less than 0.25 wt% sulfated ash.
  • an aromatic dicarboxylic acid treated dispersant supplying at least 0.30 wt. % aromatic dicarboxylic acid to said lubricating oil composition
  • an ashless peroxide decomposer present at a treat rate of from about 0.4 to 5.0 wt%; a metal deactivator wherein the metal deactivator is present at a treat rate of greater than 0.08 wt%;
  • said lubricating oil composition contains less than 1000 ppm sulfur, less than 300 ppm phosphorus and less than 0.25 wt% sulfated ash.
  • Also provided herein is a method of lubricating an engine with an ultra-low SAPS lubricating oil composition comprising:
  • aromatic dicarboxylic acid treated dispersant at least 0.30 wt. % aromatic dicarboxylic acid to said lubricating oil composition
  • an ashless peroxide decomposer present at a treat rate of from about 0.4 to 5.0 wt%; a metal deactivator wherein the metal deactivator is present at a treat rate of greater than 0.08 wt%;
  • said lubricating oil composition contains less than 1000 ppm sulfur, less than 300 ppm phosphorus and less than 0.25 wt% sulfated ash.
  • the aromatic dicarboxylic acid treated dispersant employed in the present invention is a succinimide salt of one or more aromatic dicarboxylic acids. Certain embodiments of the aromatic dicarboxylic acid treated dispersant employed in the present invention are described in published U.S. Patent Application No. 20030224948; and U.S. Patent Nos. 3,287,271; 3,692,681 ; and 3,374, 174, all of which are incorporated herein in their entirety.
  • the aromatic dicarboxylic acid treated dispersant of the present invention may comprise one or more dispersants having the general formula (1):
  • R 1 is one or more polyisobutenyl groups with a number average molecular weight of about 1100-1500
  • Z is one or more protonated poly amino radicals having from about 3 to about 7 nitrogen atoms, more preferably from about 4 to about 5 nitrogen atoms and about 8 to about 20 carbon atoms.
  • the aromatic dicarboxylic acid is preferably selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid.
  • the aromatic dicarboxyllic acid may be substituted on the aromatic ring or rings with one or more hydrocarbyl substituents such as alkyl.
  • this invention may employ a WWcombination of one or more of the aromatic dicarboxylic acids described herein.
  • the aromatic dicarboxylic acid employed in the present invention is preferably terephthalic acid.
  • the aromatic dicarboxylic acid is present in an amount in the range of about 0.30 to 10 wt %, based on the total weight of the lubricating oil composition. In one embodiment, the aromatic dicarboxylic acid is present in an amount in the range of about 0.35 to 7 wt %, based on the total weight of the lubricating oil composition. In one embodiment, the aromatic dicarboxylic acid is present in an amount in the range of about 0.40 to 5 wt %, based on the total weight of the lubricating oil composition. In one embodiment, the aromatic dicarboxylic acid is present in an amount in the range of about 0.45 to 3 wt %, based on the total weight of the lubricating oil composition. Preferably the aromatic dicarboxylic acid is present in an amount of at least 0.40 wt%, based on the total weight of the lubricating oil composition.
  • the aromatic dicarboxylic acid treated dispersant of the present invention is preferably terephthalic acid.
  • the terephthalic acid is present in the lubricating oil composition in an amount in the range of about 0.30 to 10 wt%. In one embodiment, the terephthalic acid is present in the lubricating oil composition in an amount in the range of about 0.35 to 7 wt%. In one embodiment, the terephthalic acid is present in the lubricating oil composition in an amount in the range of about 0.40 to 5 wt%. In one embodiment, the terephthalic acid is present in the lubricating oil composition in an amount in the range of about 0.45 to 3 wt%. Preferably the terephthalic acid is present in the lubricating oil composition in an amount of at least 0.40 wt%.
  • the aromatic dicarboxylic acid treated dispersant of the present invention comprise one or more succinimide salts of terephthalic acid.
  • aromatic dicarboxylic acid treated dispersant of this invention may be synthesized as described in U.S. Patent Nos. 3,287,271; 3,692,681 ; and 3,374, 174, all of which are incorporated herein in their entirety.
  • the aromatic dicarboxylic acid treated dispersant of this invention may be synthesized by reacting about 1100 to about 1500, preferably about 1300 molecular weight polyisobutenyl succinic anhydride (PIBSA) with one or more polyamines, preferably one or more heavy polyamines (HP A) at an amine/PIBSA CMR (Charge Mole Ratio) of about 0.4 to about 0.6, preferably about 0.45.
  • PIBSA polyisobutenyl succinic anhydride
  • HP A heavy polyamines
  • the aromatic dicarboxylic acid treated dispersant of this invention may be synthesized by the reaction of PIBSA with polyamine and terephthalic acid.
  • Diethylenetriamine (DETA) may be used as the polyamine in this reaction. Any polyamine may be used.
  • the aromatic dicarboxylic acid treated dispersant of this invention may be synthesized as follows.
  • One or more PIBSAs may be reacted with one or more polyamines to produce one or more succinimides by heating the mixture, with or without diluent, at a temperature of from about 1 10° C. to about 200° c, preferably about 150° C. to about 170° c, for 1 to 20 hours. Heating for about 3 to about 6 hours is preferred.
  • Reactants may be mixed and then heated or heating may occur while the reactants are being mixed. During the heating period, water of the reaction may be removed by any means known in the art. Any PIBSA may be used.
  • a mixture of PIBSA and a copolymer may also be used.
  • An amine/PIBSA charge mole ratio (CMR) of about 0.4 to 0.6 may be used.
  • a preferred CMR (Charge Mole Ratio) may be about 0.4 to about 0.5.
  • the reaction mixture may be cooled to about 1 10° C. to about 150° c, preferably about 130° C. to about 135° C.
  • Terephthalic acid may then be added.
  • terephthalic acid preferably about 2.5% to about 3.5% by weight, based on the succinimide weight
  • This mixture may then be heated for about 1 to about 10 hours, preferably about 2 to about 4 hours.
  • the mixture may then be filtered.
  • this invention may comprise one or more dispersants synthesized by reacting 1000 molecular weight polyisobutenesuccinic anhydride (PIBSA) with tetraethylenepentamine (TEPA) using an amine/PIBSA charge mole ratio (CMR) of 0.71. This produces a reaction product, which may then be reacted with terephthalic acid to form an aromatic dicarboxylic acid treated dispersant.
  • PIBSA polyisobutenesuccinic anhydride
  • TEPA tetraethylenepentamine
  • CMR charge mole ratio
  • the aromatic dicarboxylic acid treated dispersant of this invention supplying at least 0.30 wt. % aromatic dicarboxylic acid is an aromatic dicarboxylic acid treated succinimide dispersant.
  • succinmide dispersants include, but are not limited to, mono- succinamide and di-succinamide, and combinations thereof.
  • the succinmide dispersant is a polyisobutenyl succinimide.
  • the polyisobutenyl succinimide is prepared by reacting a polyalkylene polyamine and polyisobutenyl succinic anhydride under reactive conditions, wherein the polyisobutenyl group has an average molecular weight in the range of about 500 to 5,000, preferably about
  • the aromatic dicarboxylic acid treated dispersant will generally contain from 2.8 to 3.2 wt.% aromatic dicarboxylic acid.
  • Suitable polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.
  • the polyisobutenyl-succinimide may be further modified by post-treatment with an aromatic carboxylic acid, boric acid or cyclic carbonate.
  • Preferred amines for reaction to form the succinimide are polyamines having from 2 to 60 carbon atoms and from 2 to 12 nitrogen atoms per molecule, and particularly preferred are the polyalkyleneamines represented by the formula
  • n 2 to 3 and m is 0 to 10.
  • Illustrative are ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, tetrapropylene pentamine, pentaethylene hexamine and the like, as well as the commercially available mixtures of such polyamines.
  • Amines including other groups such as hydroxy, alkoxy, amide, nitride and imidazoline groups may also be used, as may polyoxyalkylene polyamines.
  • the amines are reacted with the alkenyl succinic acid or anhydride in conventional ratios of about 1 : 1 to 10: 1, preferably 1 : 1 to 3 : 1 , moles of alkenyl succinic acid or anhydride to polyamine, and preferably in a ratio of about 1 : 1, typically by heating the reactants to from 100 degree to 250 degree C, preferably 125 degree to 175 degree C, for 1 to 10, preferably 2 to 6, hours.
  • the oil soluble ashless peroxide decomposer is as described U. S. Patent Application No. 20100152079 which is incorporated in its entirety.
  • the oil soluble ashless peroxide is a compound according to formula I:
  • Ri and R2 and R3 and R4 are each independently selected from the group consisting of alkyl from 1 to 20 carbon atoms, more preferably alkyl from 1 to 10 carbon atoms and even more preferably lower alkyl from 1 to six carbon atoms.
  • the alkyl groups above can have either a straight chain or a branched chain, which are fully saturated hydrocarbon chain; for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and the like, and isomers and mixtures thereof.
  • a suitable hindered amine that may be used in the present invention is ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl- naphthalene-l,8-diamine and sold by Sigma-Aldrich as Proton-spongeTM.
  • the ⁇ , ⁇ , ⁇ ', ⁇ '- tetramethyl-naphthalene-l,8-diamine is a strained molecule due to the close proximity to the dimethylamine groups.
  • the free base is destabilized by the steric inhibition of resonance, van der Walls repulsions, and lone pair interactions.
  • strains are typically relieved by monoprotonation and formation of an intramolecular hydrogen bond and thus can effectively alter the equilibrium constant of the hydroperoxide decomposition reaction.
  • This imparts a high basicity relative to normal aliphatic amines or aromatic amines and which is necessary to deprotonate a hydroperoxide. Deprotonation of the peroxide would render the oxygen- oxygen bond more stable toward decomposition into radicals.
  • the strong basicity of the N,N,N',N'-tetramethyl-naphthalene-l,8-diamine can be ascribed to the operation of several factors, e.g.
  • ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-naphthalene- 1,8 -diamine structure is compromise involving several factors including a twist in the naphthalene ring system, favorable lone pair/ ⁇ overlap, lone pair/methyl nonbonded interactions, and lone pair/lone pair repulsion.
  • the compounds of formula I are selected with sufficient alkyl groups to be oil soluble in the lubricating composition and thus the compound of formula I are combined with an oil of lubricating viscosity.
  • concentration of the compound of formula I in the lubricating composition can vary depending upon the requirements, applications and effect or degree of synergy desired.
  • a practical ⁇ , ⁇ , ⁇ ', ⁇ '- tetraalkyl-naphthalene-l,8-diamine use range in the lubricating composition is from about 0.4 to 10.0 wt % , and preferably from 0.5 to 3.0 wt%. based on the total weight of the lubricating oil composition.
  • the ⁇ , ⁇ , ⁇ ', ⁇ '-tetraalkyl-naphthalene- 1,8 -diamine compound of formula I can be used as a complete or partial replacement for commercially available antioxidants currently used in lubricant formulations and can be in combination with other additives typically found in motor oils and fuels. When used in combination with other types of antioxidants or additives used in oil formulations, synergistic and/or additive performance effects may also be obtained with respect to improved antioxidancy, antiwear, frictional and detergency and high temperature engine deposit properties. Such other additives can be any presently known or later-discovered additives used in formulating lubricating oil
  • the lubricating oil additives typically found in lubricating oils are, for example, dispersants, detergents, corrosion/rust inhibitors, antioxidants, anti-wear agents, anti-foamants, friction modifiers, seal swell agents, emulsifiers, VI improvers, pour point depressants, and the like.
  • Hydrocarbon oxidation is a three step process which comprises:
  • Oxidative degradation and the reaction mechanisms are dependent upon the specific hydrocarbons, temperatures, operating conditions, catalysts such as metals, etc., which more detail can be found in Chapter 4 of Mortier R.M. et al, 1992, “Chemistry and Technology of Lubricants Initiation", VCH Publishers, Inc.;
  • Initiation involves the reaction of oxygen or nitrogen oxides ( O x ) on a hydrocarbon molecule. Typically, initiation starts by the abstraction of hydrocarbon proton. This may result in the formation of hydrogen peroxide (HOOH) and radicals such as alkyl radicals (R * ) and peroxy radicals (ROO * ). During the propagation stage, hydroperoxides may decompose, either on their own or in the presence of catalysts such as metal ions, to alkoxy radicals (RO * ) and peroxy radicals.
  • HOOH hydrogen peroxide
  • R * alkyl radicals
  • ROO * peroxy radicals
  • radicals can react with the hydrocarbons to form a variety of additional radicals and reactive oxygen containing compounds such as alcohols, aldehydes, ketones and carboxylic acids; which again can further polymerize or continue chain propagation. Termination results from the self termination of radicals or by reacting with oxidation inhibitors.
  • the uncatalyzed oxidation of hydrocarbons at temperatures of up to about 120° C primarily leads to alkyl-hydroperoxides, dialkylperoxides, alcohols, ketones; as well as the products which result from cleavage of dihydroperoxides such as diketones, keto-aldehydes hydroxyketones and so forth.
  • the reaction rates are increased and cleavage of the hydroperoxides plays a more important role. Since autoxidation is a free-radical chain reaction, it therefore, can be inhibited at the initiation and/or propagation steps. .
  • Hydroperoxide decomposers convert the hydroperoxides into non-radical products and thus prevent the chain propagation reaction.
  • organosulfur and organophosphorous containing additives have been employed for this purpose typically eliminating hydroperoxides via acid catalyzed decomposition or oxygen transfer.
  • increased concerns regarding total sulfur and/or phosphorous content in finished lubricating oil has led to efforts to reduce or eliminate sulfur and phosphorous in lubricant oil formulations.
  • the oil soluble ashless peroxide decomposer according to formula I is a potent decomposer which converts hydroperoxides into non-radical products and thus prevent the chain propagation reaction.
  • the oil soluble ashless peroxide decomposer compound according to formula I is effective by itself when employed in a lubricating oil composition.
  • the oil soluble ashless peroxide decomposer compound according to formula I can function as an antioxidant and can also be employed in combination with other free radical antioxidants.
  • sulfur is present in the lubricating oil composition at less than 1000 ppm, less than 800 ppm, less than 500 ppm, less than 300 ppm, less than 100 ppm less than 50 ppm, less than 10 ppm, and 0 ppm.
  • phosphorous is present in the lubricating oil composition at less than 300 ppm, less than 200 ppm, less than 100 ppm, less than 50 ppm, less than 10 ppm, and 0 ppm.
  • sulfated ash is present in the lubricating oil composition at less than 0.25 wt%, less than 0.20 wt%, less than 0.15wt%, less than 0.10 wt%, less than0.05 wt%, less than 0.01 wt%., and 0 wt.
  • the lubricating oil composition contains less than 800 ppm sulfur, less than 200 ppm phosphorous, and less than 0.20 wt% sulfated ash.
  • the lubricating oil composition contains less than 500 ppm sulfur, less than 100 ppm phosphorous, and less than 0.15 wt% sulfated ash.
  • the lubricating oil composition contains less than 300 ppm sulfur, less than 50 ppm phosphorous, and less than 0.10 wt% sulfated ash.
  • the lubricating oil composition contains less than 100 ppm sulfur, 0 ppm phosphorous, and less than 0.05 wt% sulfated ash.
  • the lubricating oil composition contains less than 50 ppm sulfur, 0 ppm phosphorous, and less than 0.05 wt% sulfated ash.
  • the lubricating oil composition comprises an ashless metal deactivator.
  • suitable metal deactivators include disalicylidene propylenediamine, triazole derivatives, thiadiazole derivatives, and mercaptobenzimidazoles.
  • the metal deactivator component of the present invention is preferably an aromatic triazole or an alkyl-substituted aromatic triazole; for example, benzotriazole, tolyltriazole, or mixtures thereof .
  • the most preferred triazole for use is tolyltriazole.
  • the metal deactivator is employed at concentrations of about 0.1 - 0.5 wt %; preferably about 0.1 - 0.4 wt. %; preferably about 0.1 - 0.3 wt. %; and more preferably about 0.1 - 0.2 wt. %.
  • Metal deactivators are useful in improving the corrosion protection of copper and copper alloys.
  • the aromatic dicarboxylic acid treated dispersant will generally contain from 2.8 to
  • the base oil of lubricating viscosity for use in the lubricating oil compositions of this invention is typically present in a major amount, e.g., an amount of greater than 50 wt. %, preferably greater than about 70 wt. %, more preferably from about 80 to about 99.5 wt. % and most preferably from about 85 to about 98 wt. %, based on the total weight of the composition.
  • base oil as used herein shall be understood to mean a base stock or blend of base stocks which is a lubricant component that is produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location); that meets the same manufacturer's specification; and that is identified by a unique formula, product identification number, or both.
  • the base oil for use herein can be any presently known or later-discovered base oil of lubricating viscosity used in formulating lubricating oil compositions for any and all such applications, e.g., engine oils, marine cylinder oils, functional fluids such as hydraulic oils, gear oils, transmission fluids, etc.
  • the base oils for use herein can optionally contain viscosity index improvers, e.g., polymeric alkylmethacrylates; olefinic copolymers, e.g., an ethylene-propylene copolymer or a styrene-butadiene copolymer; and the like and mixtures thereof.
  • viscosity index improvers e.g., polymeric alkylmethacrylates
  • olefinic copolymers e.g., an ethylene-propylene copolymer or a styrene-butadiene copolymer; and the like and mixtures thereof.
  • the viscosity of the base oil is dependent upon the application. Accordingly, the viscosity of a base oil for use herein will ordinarily range from about 2 to about 2000 centistokes (cSt) at 100° Centigrade (C).
  • the base oils used as engine oils will have a kinematic viscosity range at 100°C of about 2 cSt to about 30 cSt, preferably about 3 cSt to about 16 cSt, and most preferably about 4 cSt to about 12 cSt and will be selected or blended depending on the desired end use and the additives in the finished oil to give the desired grade of engine oil, e.g., a lubricating oil composition having an SAE Viscosity Grade of 0W, OW-16, OW-20, 0W-30, OW-40, 0W-50, OW-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 20W-40 or 20W-50.
  • Oils used as gear oils can have viscosities ranging from about 2 cSt to about 2000 cSt at 100°
  • Base stocks may be manufactured using a variety of different processes including, but not limited to, distillation, solvent refining, hydrogen processing, oligomerization, esterification, and rerefining. Rerefined stock shall be substantially free from materials introduced through manufacturing, contamination, or previous use.
  • the base oil of the lubricating oil compositions of this invention may be any natural or synthetic lubricating base oil.
  • Suitable hydrocarbon synthetic oils include, but are not limited to, oils prepared from the polymerization of ethylene or from the polymerization of 1 -olefins to provide polymers such as polyalphaolefin or PAO oils, or from hydrocarbon synthesis procedures using carbon monoxide and hydrogen gases such as in a Fischer-Tropsch process.
  • a suitable base oil is one that comprises little, if any, heavy fraction; e.g., little, if any, lube oil fraction of viscosity 20 cSt or higher at 100°C.
  • the base oil may be derived from natural lubricating oils, synthetic lubricating oils or mixtures thereof.
  • Suitable base oil includes base stocks obtained by isomerization of synthetic wax and slack wax, as well as hydrocracked base stocks produced by hydrocracking (rather than solvent extracting) the aromatic and polar components of the crude.
  • Suitable base oils include those in all API categories I, II, III, IV and V as defined in API Publication 1509, 14th Edition, Addendum I, Dec. 1998.
  • Group IV base oils are polyalphaolefins (PAO).
  • Group V base oils include all other base oils not included in Group I, II, III, or IV.
  • Group II, III and IV base oils are preferred for use in this invention, these base oils may be prepared by combining one or more of Group I, II, III, IV and V base stocks or base oils.
  • Useful natural oils include mineral lubricating oils such as, for example, liquid petroleum oils, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types, oils derived from coal or shale, animal oils, vegetable oils (e.g., rapeseed oils, castor oils and lard oil), and the like.
  • Useful synthetic lubricating oils include, but are not limited to, hydrocarbon oils and halo-substituted hydrocarbon oils such as polymerized and interpolymerized olefins, e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(l-hexenes), poly(l -octenes), poly(l-decenes), and the like and mixtures thereof; alkylbenzenes such as dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2- ethylhexyl)-benzenes, and the like; polyphenyls such as biphenyls, terphenyls, alkylated polyphenyls, and the like; alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivative, analogs
  • oils include, but are not limited to, oils made by polymerizing olefins of less than 5 carbon atoms such as ethylene, propylene, butylenes, isobutene, pentene, and mixtures thereof. Methods of preparing such polymer oils are well known to those skilled in the art.
  • Additional useful synthetic hydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity.
  • Especially useful synthetic hydrocarbon oils are the hydrogenated liquid oligomers of Ce to C 12 alpha olefins such as, for example, 1-decene trimer.
  • Another class of useful synthetic lubricating oils include, but are not limited to, alkylene oxide polymers, i.e., homopolymers, interpolymers, and derivatives thereof where the terminal hydroxyl groups have been modified by, for example, esterification or etherification.
  • oils are exemplified by the oils prepared through polymerization of ethylene oxide or propylene oxide, the alkyl and phenyl ethers of these polyoxyalkylene polymers (e.g., methyl poly propylene glycol ether having an average molecular weight of 1,000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, diethyl ether of polypropylene glycol having a molecular weight of 1,000-1,500, etc.) or mono- and polycarboxylic esters thereof such as, for example, the acetic esters, mixed C3-C8 fatty acid esters, or the C 13 oxo acid diester of tetraethylene glycol.
  • the alkyl and phenyl ethers of these polyoxyalkylene polymers e.g., methyl poly propylene glycol ether having an average molecular weight of 1,000, diphenyl ether of polyethylene glycol having a molecular weight of 500-1000, die
  • Yet another class of useful synthetic lubricating oils include, but are not limited to, the esters of dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acids, alkyl malonic acids, alkenyl malonic acids, etc., with a variety of alcohols, e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.
  • dicarboxylic acids e.g., phthalic acid, succinic acid, alkyl succinic acids, alkenyl succinic acids, maleic acid, azelaic acid, suberic acid, sebacic acid, fuma
  • esters include dibutyl adipate, di(2-ethylhexyl)sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2- ethylhexanoic acid and the like.
  • Esters useful as synthetic oils also include, but are not limited to, those made from carboxylic acids having from about 5 to about 12 carbon atoms with alcohols, e.g., methanol, ethanol, etc., polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol, tripentaerythritol, and the like.
  • Silicon-based oils such as, for example, polyalkyl-, polyaryl-, polyalkoxy- or polyaryloxy-siloxane oils and silicate oils, comprise another useful class of synthetic lubricating oils. Specific examples of these include, but are not limited to, tetraethyl silicate, tetra-isopropyl silicate, tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-hexyl)silicate, tetra-(p- tert-butylphenyl)silicate, hexyl-(4-methyl-2-pentoxy)disiloxane, poly(methyl)siloxanes, poly(methylphenyl)siloxanes, and the like.
  • Still yet other useful synthetic lubricating oils include, but are not limited to, liquid esters of phosphorous containing acids, e.g., tricresyl phosphate, trioctyl phosphate, diethyl ester of decane phosphionic acid, etc., polymeric tetrahydrofurans and the like.
  • the lubricating oil may be derived from unrefined, refined and rerefined oils, either natural, synthetic or mixtures of two or more of any of these of the type disclosed hereinabove.
  • Unrefined oils are those obtained directly from a natural or synthetic source (e.g., coal, shale, or tar sands bitumen) without further purification or treatment.
  • Examples of unrefined oils include, but are not limited to, a shale oil obtained directly from retorting operations, a petroleum oil obtained directly from distillation or an ester oil obtained directly from an esterification process, each of which is then used without further treatment.
  • Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties.
  • These purification techniques are known to those of skill in the art and include, for example, solvent extractions, secondary distillation, acid or base extraction, filtration, percolation, hydrotreating, dewaxing, etc.
  • Rerefined oils are obtained by treating used oils in processes similar to those used to obtain refined oils.
  • Such rerefined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques directed to removal of spent additives and oil breakdown products.
  • Lubricating oil base stocks derived from the hydroisomerization of wax may also be used, either alone or in combination with the aforesaid natural and/or synthetic base stocks.
  • Such wax isomerate oil is produced by the hydroisomerization of natural or synthetic waxes or mixtures thereof over a hydroisomerization catalyst.
  • Natural waxes are typically the slack waxes recovered by the solvent dewaxing of mineral oils; synthetic waxes are typically the wax produced by the Fischer-Tropsch process.
  • LUBRICATING OIL ADDITIVES are typically the wax produced by the Fischer-Tropsch process.
  • the lubricating oil compositions of the present invention may also contain other conventional additives for imparting auxiliary functions to give a finished lubricating oil composition in which these additives are dispersed or dissolved.
  • the lubricating oil compositions can be blended with antioxidants, anti-wear agents, ashless dispersants, detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, package compatibilisers, corrosion-inhibitors, dyes, extreme pressure agents and the like and mixtures thereof.
  • antioxidants antioxidants, anti-wear agents, ashless dispersants, detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, package compatibilisers, corrosion-inhibitors, dyes, extreme pressure agents and the like and mixtures thereof.
  • additives are known and commercially available.
  • antioxidants include, but are not limited to, aminic types, e.g., diphenylamine, phenyl-alpha-napthyl-amine, N,N-di(alkylphenyl) amines; and alkylated phenylene-diamines; phenolics such as, for example, BHT, sterically hindered alkyl phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol and 2,6-di-tert-butyl-4-(2-octyl-3- propanoic) phenol; and mixtures thereof.
  • the antioxidants of the present invention can be aminic, phenolic, or mixtures thereof.
  • antiwear agents include, but are not limited to, zinc dialkyldithiophosphates and zinc diaryldithiophosphates, e.g., those described in an article by Born et al. entitled “Relationship between Chemical Structure and Effectiveness of Some Metallic Dialkyl- and Diaryl-dithiophosphates in Different Lubricated Mechanisms", appearing in Lubrication Science 4-2 January 1992, see for example pages 97-100; aryl phosphates and phosphites, sulfur-containing esters, phosphosulfur compounds, metal or ash- free dithiocarbamates, xanthates, alkyl sulfides and the like and mixtures thereof.
  • ashless dispersants include, but are not limited to, amines, alcohols, amides, or ester polar moieties attached to the polymer backbones via bridging groups.
  • An ashless dispersant of the present invention may be, for example, selected from oil soluble salts, esters, amino-esters, amides, imides, and oxazolines of long chain hydrocarbon substituted mono and dicarboxylic acids or their anhydrides; thiocarboxylate derivatives of long chain hydrocarbons, long chain aliphatic hydrocarbons having a polyamine attached directly thereto; and Mannich condensation products formed by condensing a long chain substituted phenol with formaldehyde and polyalkylene polyamine.
  • Carboxylic dispersants are reaction products of carboxylic acylating agents (acids, anhydrides, esters, etc.) comprising at least about 34 and preferably at least about 54 carbon atoms with nitrogen containing compounds (such as amines), organic hydroxy compounds (such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols), and/or basic inorganic materials.
  • carboxylic acylating agents as acids, anhydrides, esters, etc.
  • nitrogen containing compounds such as amines
  • organic hydroxy compounds such as aliphatic compounds including monohydric and polyhydric alcohols, or aromatic compounds including phenols and naphthols
  • basic inorganic materials include imides, amides, and esters.
  • Succinimide dispersants are a type of carboxylic dispersant. They are produced by reacting hydrocarbyl-substituted succinic acylating agent with organic hydroxy compounds, or with amines comprising at least one hydrogen atom attached to a nitrogen atom, or with a mixture of the hydroxy compounds and amines.
  • succinic acylating agent refers to a hydrocarbon-substituted succinic acid or a succinic acid-producing compound, the latter encompasses the acid itself.
  • Such materials typically include hydrocarbyl-substituted succinic acids, anhydrides, esters (including half esters) and halides.
  • Succinic -based dispersants have a wide variety of chemical structures.
  • One class of succinic-based dispersants may be represented by the formula:
  • each R 1 is independently a hydrocarbyl group, such as a polyolefin-derived group.
  • the hydrocarbyl group is an alkyl group, such as a polyisobutyl group.
  • R 1 groups can contain about 40 to about 500 carbon atoms, and these atoms may be present in aliphatic forms.
  • R 2 is an alkylene group, commonly an ethylene (C 2 H 4 ) group.
  • succinimide dispersants include those described in, for example, U.S. Patent Nos. 3, 172,892, 4,234,435 and 6, 165,235.
  • the polyalkenes from which the substituent groups are derived are typically homopolymers and interpolymers of polymerizable olefin monomers of 2 to about 16 carbon atoms, and usually 2 to 6 carbon atoms.
  • the amines which are reacted with the succinic acylating agents to form the carboxylic dispersant composition can be monoamines or polyamines.
  • Succinimide dispersants are referred to as such since they normally contain nitrogen largely in the form of imide functionality, although the amide functionality may be in the form of amine salts, amides, imidazolines as well as mixtures thereof.
  • a succinimide dispersant one or more succinic acid-producing compounds and one or more amines are heated and typically water is removed, optionally in the presence of a substantially inert organic liquid solvent/diluent.
  • the reaction temperature can range from about 80°C up to the decomposition temperature of the mixture or the product, which typically falls between about 100°C to about 300°C. Additional details and examples of procedures for preparing the succinimide dispersants of the present invention include those described in, for example, U.S. Patent Nos. 3,172,892, 3,219,666, 3,272,746, 4,234,435, 6, 165,235 and 6,440,905.
  • Suitable ashless dispersants may also include amine dispersants, which are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines.
  • amine dispersants include those described in, for example, U.S. Patent Nos. 3,275,554, 3,438,757, 3,454,555 and 3,565,804.
  • Suitable ashless dispersants may further include "Mannich dispersants," which are reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). Examples of such dispersants include those described in, for example, U.S. Patent Nos. 3,036,003, 3,586,629. 3,591,598 and 3,980,569.
  • Suitable ashless dispersants may also be post-treated ashless dispersants such as post-treated succinimides, e.g., post-treatment processes involving borate or ethylene carbonate as disclosed in, for example, U.S. Patent Nos. 4,612, 132 and 4,746,446; and the like as well as other post-treatment processes.
  • the carbonate-treated alkenyl succinimide is a polybutene succinimide derived from polybutenes having a molecular weight of about 450 to about 3000, preferably from about 900 to about 2500, more preferably from about 1300 to about 2400, and most preferably from about 2000 to about 2400, as well as mixtures of these molecular weights.
  • it is prepared by reacting, under reactive conditions, a mixture of a polybutene succinic acid derivative, an unsaturated acidic reagent copolymer of an unsaturated acidic reagent and an olefin, and a polyamine, such as disclosed in U.S. Patent No. 5,716,912, the contents of which are incorporated herein by reference.
  • Borated dispersants may be formed by boronating (borating) an ashless dispersant having basic nitrogen and/or at least one hydroxyl group in the molecule, such as a succinimide dispersant, succinamide dispersant, succinic ester dispersant, succinic ester-amide dispersant, Mannich base dispersant, or hydrocarbyl amine or polyamine dispersant.
  • succinimide dispersant such as a succinimide dispersant, succinamide dispersant, succinic ester dispersant, succinic ester-amide dispersant, Mannich base dispersant, or hydrocarbyl amine or polyamine dispersant.
  • Suitable ashless dispersants may also be polymeric, which are interpolymers of oil- solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substitutes.
  • polymeric dispersants include those described in, for example, U.S. Patent Nos. 3,329,658; 3,449,250 and 3,666,730.
  • an ashless dispersant for use in the lubricating oil composition is a bis-succinimide derived from a polyisobutenyl group having a number average molecular weight of about 700 to about 2300.
  • the dispersant(s) for use in the lubricating oil compositions of the present invention are preferably non-polymeric (e g., are mono- or bis-succinimides).
  • the one or more ashless dispersants are present in the lubricating oil composition in an amount ranging from about 0.01 wt. % to about 20 wt. %, based on the total weight of the lubricating oil composition.
  • metal detergents include sulphonates, alkylphenates, sulfurized alkyl phenates, carboxylates, salicylates, phosphonates, and phosphinates.
  • Commercial products are generally referred to as neutral or overbased.
  • Overbased metal detergents are generally produced by carbonating a mixture of hydrocarbons, detergent acid, for example: sulfonic acid, alkylphenol, carboxylate etc., metal oxide or hydroxides (for example calcium oxide or calcium hydroxide) and promoters such as xylene, methanol and water.
  • detergent acid for example: sulfonic acid, alkylphenol, carboxylate etc.
  • metal oxide or hydroxides for example calcium oxide or calcium hydroxide
  • promoters such as xylene, methanol and water.
  • the calcium oxide or hydroxide reacts with the gaseous carbon dioxide to form calcium carbonate.
  • the sulfonic acid is neutralized with an excess of CaO or Ca(OH)2, to form the sul
  • Metal-containing or ash-forming detergents function as both detergents to reduce or remove deposits and as acid neutralizers or rust inhibitors, thereby reducing wear and corrosion and extending engine life.
  • Detergents generally comprise a polar head with a long hydrophobic tail.
  • the polar head comprises a metal salt of an acidic organic compound.
  • the salts may contain a substantially stoichiometric amount of the metal in which case they are usually described as normal or neutral salts, and would typically have a total base number or TBN (as can be measured by ASTM D2896) of from 0 to about 80.
  • TBN total base number
  • a large amount of a metal base may be incorporated by reacting excess metal compound (e.g., an oxide or hydroxide) with an acidic gas (e.g., carbon dioxide).
  • the resulting overbased detergent comprises neutralized detergent as the outer layer of a metal base (e.g., carbonate) micelle.
  • a metal base e.g., carbonate
  • Such overbased detergents may have a TBN of about 150 or greater, and typically will have a TBN of from about 250 to about 450 or more.
  • Detergents that may be used include oil-soluble neutral and overbased sulfonates, phenates, sulfurized phenates, thiophosphonates, salicylates, and naphthenates and other oil- soluble carboxylates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
  • a metal particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
  • the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
  • Particularly convenient metal detergents are neutral and overbased calcium sulfonates having TBN of from about 20 to about 450, neutral and overbased calcium phenates and sulfurized phenates having TBN of from about 50 to about 450 and neutral and overbased magnesium or calcium salicylates having a TBN of from about 20 to about 450.
  • Combinations of detergents, whether overbased or neutral or both, may be used.
  • the detergent can be one or more alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid.
  • Suitable hydroxyaromatic compounds include mononuclear monohydroxy and polyhydroxy aromatic hydrocarbons having 1 to 4, and preferably 1 to 3, hydroxyl groups.
  • Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.
  • the preferred hydroxyaromatic compound is phenol.
  • the alkyl substituted moiety of the alkali or alkaline earth metal salt of an alkyl- substituted hydroxyaromatic carboxylic acid is derived from an alpha olefin having from about 10 to about 80 carbon atoms.
  • the olefins employed may be linear, isomerized linear, branched or partially branched linear.
  • the olefin may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a mixture of partially branched linear or a mixture of any of the foregoing.
  • the mixture of linear olefins that may be used is a mixture of normal alpha olefins selected from olefins having from about 12 to about 30 carbon atoms per molecule.
  • the normal alpha olefins are isomerized using at least one of a solid or liquid catalyst.
  • the olefins are a branched olefinic propylene oligomer or mixture thereof having from about 20 to about 80 carbon atoms, i.e., branched chain olefins derived from the polymerization of propylene.
  • the olefins may also be substituted with other functional groups, such as hydroxy groups, carboxylic acid groups, heteroatoms, and the like.
  • the branched olefinic propylene oligomer or mixtures thereof have from about 20 to about 60 carbon atoms.
  • the branched olefinic propylene oligomer or mixtures thereof have from about 20 to about 40 carbon atoms.
  • the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is an alkali or alkaline earth metal salt of an alkyl- substituted hydroxybenzoic acid that is derived from an alkyl-substituted hydroxybenzoic acid in which the alkyl groups are the residue of normal alpha-olefins containing at least 75 mole% C2 0 or higher normal alpha-olefins.
  • At least about 50 mole % (e.g., at least about 60 mole %, at least about 70 mole %, at least about 80 mole %, at least about 85 mole %, at least about 90 mole %, at least about 95 mole %, or at least about 99 mole %) of the alkyl groups contained within the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid such as the alkyl groups of an alkali or alkaline earth metal salt of an alkyl- substituted hydroxybenzoic acid are about C 4 to about Cis.
  • the resulting alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid will be a mixture of ortho and para isomers.
  • the product will contain about 1 to 99% ortho isomer and 99 to 1% para isomer.
  • the product will contain about 5 to 70% ortho and 95 to 30% para isomer.
  • the alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid can be neutral or overbased.
  • an overbased alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is one in which the BN of the alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid has been increased by a process such as the addition of a base source (e.g., lime) and an acidic overbasing compound (e.g., carbon dioxide).
  • Overbased salts may be low overbased, e.g., an overbased salt having a BN below about 100.
  • the BN of a low overbased salt may be from about 5 to about 50. In another embodiment, the BN of a low overbased salt may be from about 10 to about 30. In yet another embodiment, the BN of a low overbased salt may be from about 15 to about 20.
  • Overbased detergents may be medium overbased, e.g., an overbased salt having a BN from about 100 to about 250.
  • the BN of a medium overbased salt may be from about 100 to about 200.
  • the BN of a medium overbased salt may be from about 125 to about 175.
  • Overbased detergents may be high overbased, e.g., an overbased salt having a BN above about 250.
  • the BN of a high overbased salt may be from about 250 to about 450.
  • Sulfonates may be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples included those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives.
  • the alkylation may be carried out in the presence of a catalyst with alkylating agents having from about 3 to more than 70 carbon atoms.
  • the alkaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms per alkyl substituted aromatic moiety.
  • the oil soluble sulfonates or alkaryl sulfonic acids may be neutralized with oxides, hydroxides, alkoxides, carbonates, carboxylate, sulfides, hydrosulfides, nitrates, borates and ethers of the metal.
  • the amount of metal compound is chosen having regard to the desired TBN of the final product but typically ranges from about 100 to about 220 wt. % (preferably at least about 125 wt. %) of that stoichiometrically required.
  • Metal salts of phenols and sulfurized phenols are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide and neutral or overbased products may be obtained by methods well known in the art.
  • Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form products which are generally mixtures of compounds in which 2 or more phenols are bridged by sulfur containing bridges.
  • sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide
  • the one or more detergents are present in the lubricating oil composition in an amount ranging from about 0.01 wt. % to about 10 wt. %, based on the total weight of the lubricating oil composition.
  • rust inhibitors include, but are not limited to, nonionic polyoxyalkylene agents, e.g., polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene octyl stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol monooleate, and polyethylene glycol monooleate; stearic acid and other fatty acids; dicarboxylic acids; metal soaps; fatty acid amine salts; metal salts of heavy sulfonic acid; partial carboxylic acid ester of polyhydric alcohol; phosphoric esters; (short- chain) alkenyl succinic acids; partial esters thereof and nitrogen-containing derivatives thereof; synthetic alkarylsulfonates, e.g., metal dinonylnaphthalene sulfon
  • friction modifiers include, but are not limited to, alkoxylated fatty amines; borated fatty epoxides; fatty phosphites, fatty epoxides, fatty amines, borated alkoxylated fatty amines, metal salts of fatty acids, fatty acid amides, glycerol esters, borated glycerol esters; and fatty imidazolines as disclosed in U.S. Patent No.
  • friction modifiers obtained from a reaction product of a C 4 to C75, preferably a Ce to C24, and most preferably a Ce to C20, fatty acid ester and a nitrogen-containing compound selected from the group consisting of ammonia, and an alkanolamine and the like and mixtures thereof.
  • antifoaming agents include, but are not limited to, polymers of alkyl methacrylate; polymers of dimethyls ilicone and the like and mixtures thereof.
  • a pour point depressant examples include, but are not limited to, polymethacrylates, alkyl acrylate polymers, alkyl methacrylate polymers, di(tetra-paraffin phenol)phthalate, condensates of tetra-paraffin phenol, condensates of a chlorinated paraffin with naphthalene and combinations thereof.
  • a pour point depressant comprises an ethylene-vinyl acetate copolymer, a condensate of chlorinated paraffin and phenol, polyalkyl styrene and the like and combinations thereof.
  • the amount of the pour point depressant may vary from about 0.01 wt. % to about 10 wt. %.
  • demulsifier examples include, but are not limited to, anionic surfactants (e.g., alkyl-naphthalene sulfonates, alkyl benzene sulfonates and the like), nonionic alkoxylated alkylphenol resins, polymers of alkylene oxides (e.g., polyethylene oxide, polypropylene oxide, block copolymers of ethylene oxide, propylene oxide and the like), esters of oil soluble acids, polyoxyethylene sorbitan ester and the like and combinations thereof.
  • the amount of the demulsifier may vary from about 0.01 wt. % to about 10 wt. %.
  • Examples of a corrosion inhibitor include, but are not limited to, half esters or amides of dodecylsuccinic acid, phosphate esters, thiophosphates, alkyl imidazolines, sarcosines and the like and combinations thereof.
  • the amount of the corrosion inhibitor may vary from about 0.01 wt. % to about 5 wt. %.
  • the corrosion inhibitor component can be a non-polycarboxylate moiety containing thiadiazole.
  • the thiadiazole comprises at least one of 2,5-dimercapto-l,3,4- thiadiazole; 2-mercapto-5-hydrocarbylthio- 1 ,3,4-thiadiazoles; 2-mercapto-5- hydrocarbyldithio-l,3,4-thiadiazoles; 2,5-bis(hydrocarbylthio and 2,5-bis(hydrocarbyldithio)- 1,3,4-thiadiazoles.
  • the more preferred compounds are the 1,3,4-thiadiazoles, especially the 2-hydrocarbyldithio-5-mercapto-l,3,4-dithiadiazoles and the 2,5-bis(hydrocarbyldithio)- 1,3,4-thiadiazoles, a number of which are available as articles of commerce.
  • a non polycarboxylate containing thiadiazole containing about 4.0 wt% 2,5-dimercapto-l,3,4- thiadiazole which may be either Ethyl Corporation's Hitec® 4313 or Lubrizol Corporation's Lubrizol® 5955A, is used.
  • Hitec® 4313 may be obtained from Ethyl Corporation,
  • an extreme pressure agent examples include, but are not limited to, sulfurized animal or vegetable fats or oils, sulfurized animal or vegetable fatty acid esters, fully or partially esterified esters of trivalent or pentavalent acids of phosphorus, sulfurized olefins, dihydrocarbyl polysulfides, sulfurized Diels-Alder adducts, sulfurized dicyclopentadiene, sulfurized or co-sulfurized mixtures of fatty acid esters and monounsaturated olefins, co- sulfurized blends of fatty acid, fatty acid ester and alpha-olefin, functionally-substituted dihydrocarbyl polysulfides, thia-aldehydes, thia-ketones, epithio compounds, sulfur- containing acetal derivatives, co-sulfurized blends of terpene and acyclic olefins, and polysulfide olefin products, amine salts of
  • each of the foregoing additives when used, is used at a functionally effective amount to impart the desired properties to the lubricant.
  • a functionally effective amount of this friction modifier would be an amount sufficient to impart the desired friction modifying characteristics to the lubricant.
  • the concentration of each of these additives, when used may range, unless otherwise specified, from about 0.001% to about 20% by weight, and in one embodiment about 0.01% to about 10% by weight based on the total weight of the lubricating oil composition.
  • the lubricating oil additives of the present invention may be provided as an additive package or concentrate in which the additives are incorporated into a substantially inert, normally liquid organic diluent such as, for example, mineral oil, naphtha, benzene, toluene or xylene to form an additive concentrate.
  • a substantially inert, normally liquid organic diluent such as, for example, mineral oil, naphtha, benzene, toluene or xylene to form an additive concentrate.
  • These concentrates usually contain from about 20% to about 80% by weight of such diluent.
  • a neutral oil having a viscosity of about 4 to about 8.5 cSt at 100°C and preferably about 4 to about 6 cSt at 100°C will be used as the diluent, though synthetic oils, as well as other organic liquids which are compatible with the additives and finished lubricating oil can also be used.
  • Baseline performance is exemplified by a standard GF-5 oil. This oil has SAPS levels near the mandated limit: sulfur of 0.2 wt%, phosphorus of 0.075 wt% and sulfated ash of 1.1 wt%. When all additives contributing to SAPS levels were removed (Ultra-Low SAPS oil
  • HTCBT High Temperature Corrosion Bench Test
  • BRT Ball Rust Test
  • TEOST MHT-4 Thermo-oxidation engine oil simulation test at moderately high temperature
  • Passing levels for the HTCBT are: Copper are less than 20 ppm; and Lead less than 120 ppm.
  • BRT Ball Rust Test ASTM D6557 (Version 10a). Passing for the BRT is greater than 100 Average Grey Value (AVG).
  • Aromatic dicarboxylic acid treated dispersant An oil concentrate of aromatic dicarboxylic acid treated succinimide. Comparative example H has 0.23 wt% acid from the aromatic dicarboxylic acid treated succinimide dispersant. Inventive example 1 has 0.46 wt% acid from the aromatic dicarboxylic acid treated succinimide dispersant.
  • Dispersant A An oil concentrate of ethylene carbonate-treated succinimide derived from 2300 MW PIBSA and heavy polyamine (HP A).
  • Dispersant B A succinimide synthesized from 2300 MW PIBSA and heavy polyamine (HP A).
  • Decomposer The ashless peroxide decomposer according to Formula I in the present specification.
  • Table 3 is a Pass / Fail summary of Comparative Examples A to H and Inventive Example 1 in the HT CBT (Cu, Pb), BRT and TEOST tests.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

La présente invention se rapporte à une composition d'huile de lubrification à ultra faible teneur en cendres sulfatées, phosphore et soufre, qui comprend : une huile ayant une viscosité de lubrification ; un dispersant traité par un acide dicarboxylique aromatique qui fournit au moins 0,30 % en poids de l'acide dicarboxylique aromatique à ladite composition d'huile de lubrification ; un décomposeur de peroxyde sans cendres présent à un taux de traitement allant d'environ 0,4 à 5,0 % en poids ; un désactivateur métallique présent à un taux de traitement supérieur à 0,08 % en poids ; ladite composition d'huile de lubrification contenant une quantité de soufre inférieure à 1 000 ppm, une quantité de phosphore inférieure à 300 ppm et une quantité de cendres sulfatées inférieure à 0,25 % en poids.
EP13867703.4A 2012-12-28 2013-11-22 Lubrifiants à ultra faible teneur en cendres sulfatées, phosphore et soufre pour des moteurs à combustion interne Withdrawn EP2938713A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13/729,465 US20140187455A1 (en) 2012-12-28 2012-12-28 Ultra-low saps lubricants for internal combustion engines
PCT/US2013/071503 WO2014105311A2 (fr) 2012-12-28 2013-11-22 Lubrifiants à ultra faible teneur en cendres sulfatées, phosphore et soufre pour des moteurs à combustion interne

Publications (2)

Publication Number Publication Date
EP2938713A2 true EP2938713A2 (fr) 2015-11-04
EP2938713A4 EP2938713A4 (fr) 2016-01-27

Family

ID=51017842

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13867703.4A Withdrawn EP2938713A4 (fr) 2012-12-28 2013-11-22 Lubrifiants à ultra faible teneur en cendres sulfatées, phosphore et soufre pour des moteurs à combustion interne

Country Status (8)

Country Link
US (1) US20140187455A1 (fr)
EP (1) EP2938713A4 (fr)
JP (1) JP6023353B2 (fr)
KR (1) KR20150099824A (fr)
CN (1) CN104884590A (fr)
CA (1) CA2893850C (fr)
SG (1) SG11201505003RA (fr)
WO (1) WO2014105311A2 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112018003276A2 (pt) * 2015-08-20 2018-09-25 Lubrizol Corp derivados de azol como aditivos lubrificantes
JP6741239B2 (ja) * 2016-03-28 2020-08-19 出光興産株式会社 潤滑油組成物
US11319634B2 (en) 2019-12-16 2022-05-03 Saudi Arabian Oil Company Corrosion inhibitors for a refinery
US11345872B2 (en) * 2020-01-30 2022-05-31 ExxonMobil Technology and Engineering Company Sulfur-free, ashless, low phosphorus lubricant compositions with improved oxidation stability
US11046901B1 (en) 2020-06-15 2021-06-29 Saudi Arabian Oil Company Naphthenic acid corrosion inhibitors for a refinery
US11434413B1 (en) 2021-05-07 2022-09-06 Saudi Arabian Oil Company Flourinated aromatic compound as refinery corrosion inhibitor
US20240199969A1 (en) * 2022-12-20 2024-06-20 Afton Chemical Corporation Low ash lubricating compositions for controlling steel corrosion

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3287271A (en) * 1965-01-21 1966-11-22 Chevron Res Combined detergent-corrosion inhibitors
US3692681A (en) * 1968-08-02 1972-09-19 Chevron Res Dispersion of terephthalic acid in detergent containing hydrocarbon oil medium
JP3980146B2 (ja) * 1998-01-13 2007-09-26 シェブロンジャパン株式会社 潤滑油添加剤組成物及び潤滑油組成物
GB0021041D0 (en) 2000-08-29 2000-10-11 Exxonmobil Res & Eng Co Low phosphorus lubricating oil composition
EP1439217B1 (fr) * 2001-10-12 2012-06-20 Nippon Oil Corporation Composition d'huile de lubrification pour un moteur a combustion
US7026273B2 (en) * 2001-11-09 2006-04-11 Infineum International Limited Lubricating oil compositions
US6730638B2 (en) * 2002-01-31 2004-05-04 Exxonmobil Research And Engineering Company Low ash, low phosphorus and low sulfur engine oils for internal combustion engines
US20030224948A1 (en) * 2002-02-14 2003-12-04 Dam Willem Van Lubricating oil additive comprising EC-treated succinimide, borated dispersant and corrosion inhibitor
MY145889A (en) 2004-07-08 2012-05-15 Shell Int Research Lubricating oil composition
CN101090958B (zh) * 2004-11-24 2011-12-21 新日本石油株式会社 润滑油组合物
US20100160191A1 (en) * 2006-09-01 2010-06-24 The Lubrizol Corporation Lubricating Composition
US8022021B2 (en) * 2007-02-05 2011-09-20 The Lubrizol Corporation Low ash controlled release gels
WO2008147700A1 (fr) * 2007-05-24 2008-12-04 The Lubrizol Corporation Composition lubrifiante contenant du soufre, du phosphore et un agent anti-usure sans cendres et un agent de modification du frottement contenant une amine
CA2690200C (fr) * 2007-06-08 2014-09-30 Infineum International Limited Additifs et compositions d'huiles de graissage les contenant
US8623798B2 (en) * 2007-12-20 2014-01-07 Chevron Oronite Company Llc Lubricating oil compositions containing a tetraalkyl-napthalene-1,8 diamine antioxidant
US7833954B2 (en) * 2008-02-11 2010-11-16 Afton Chemical Corporation Lubricating composition
US8242066B2 (en) * 2008-12-23 2012-08-14 Infineum International Limited Aniline compounds as ashless TBN sources and lubricating oil compositions containing same
KR20120099065A (ko) * 2009-12-03 2012-09-06 이데미쓰 고산 가부시키가이샤 윤활유 조성물

Also Published As

Publication number Publication date
CA2893850C (fr) 2020-08-04
SG11201505003RA (en) 2015-07-30
US20140187455A1 (en) 2014-07-03
EP2938713A4 (fr) 2016-01-27
KR20150099824A (ko) 2015-09-01
WO2014105311A2 (fr) 2014-07-03
JP6023353B2 (ja) 2016-11-09
WO2014105311A3 (fr) 2014-10-23
CN104884590A (zh) 2015-09-02
CA2893850A1 (fr) 2014-07-03
JP2016505687A (ja) 2016-02-25

Similar Documents

Publication Publication Date Title
CA2893850C (fr) Lubrifiants a ultra faible teneur en cendres sulfatees, phosphore et soufre pour des moteurs a combustion interne
EP2665705B1 (fr) Procédé de préparation amélioré de complexes de succinimide de molybdène de faible poids moléculaire
EP2633012B1 (fr) Utilisation et méthode pour réduire les dépôts dans les soupapes d'admission d'un moteur
EP2665718B1 (fr) Procédé de préparation amélioré de complexes de succinimide de molybdène de poids moléculaire élevé
EP2938712B1 (fr) Lubrifiants à ultra-faible teneur en cendres sulfatées, en phosphore et en soufre (saps) pour des moteurs à combustion interne
US20120247412A1 (en) Method for improving fuel economy of a heavy duty diesel engine
EP2553060B1 (fr) Utilisation de composé de titan pour améliorer la performance contre la corrosion du cuivre
EP2553061B1 (fr) Utilisation d'un composé de titane pour améliorer la compatibilité d'un joint en élastomère fluorocarboné

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20150528

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

A4 Supplementary search report drawn up and despatched

Effective date: 20160105

RIC1 Information provided on ipc code assigned before grant

Ipc: C10N 60/00 20060101ALN20151221BHEP

Ipc: C10N 30/10 20060101ALN20151221BHEP

Ipc: C10M 141/12 20060101ALI20151221BHEP

Ipc: C10N 40/25 20060101ALN20151221BHEP

Ipc: C10N 30/12 20060101ALN20151221BHEP

Ipc: C10M 129/34 20060101AFI20151221BHEP

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20180413

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20180626